Biodurability of single-walled carbon nanotubes depends on surface functionalization

Recent research has led to increased concern about the potential adverse human health impacts of carbon nanotubes, and further work is needed to better characterize those risks and develop risk management strategies. One of the most important determinants of the chronic pathogenic potential of a respirable fiber is its biological durability, which affects the long-term dose retained in the lungs, or biopersistence. The present article characterizes the biodurability of single-walled carbon nanotubes using an in vitro assay simulating the phagolysosome. Biodurability is observed to depend on the chemistry of nanotube surface functionalization. Single-walled nanotubes with carboxylated surfaces are unique in their ability to undergo 90-day degradation in a phagolysosomal simulant leading to length reduction and accumulation of ultrafine solid carbonaceous debris. Unmodified, ozone-treated, and aryl-sulfonated tubes do not degrade under these conditions. We attribute the difference to the unique chemistry of acid carboxylation, which not only introduces COOH surface groups, but also causes collateral damage to the tubular graphenic backbone in the form of neighboring active sites that provide points of attack for further oxidative degradation. These results suggest the strategic use of surface carboxylation in nanotube applications where biodegradation may improve safety or add function.     

Rapid surface functionalization of iron-filled multi-walled carbon nanotubes

Iron-filled multi-walled carbon nanotubes (Fe@MWCNTs) were surface functionalized with various functionalities via a rapid, single-step process involving ultrasonication assisted and microwave-induced radical polymerization reactions. Both hydrophobic (e.g., polystyrenes and polymethyl methacrylate) and hydrophilic (e.g., polyacrylamide, polyacrylic acids, and polyallyl alcohols) polymer chains can be chemically grafted onto the surface of MWCNTs by the same process within 10 min. The surface grafted polymers were identified by FTIR, TGA, TEM, EELS and Raman spectra. The solubilities of the surface derivatized MWCNTs are in the range of 1200–2800 mg/l in solutions. The polyacrylic acids modified iron filled MWCNTs have a saturated magnetic dipole moment of 40 emu/g at room temperature with a coerceive field of nearly zero gauss.     

Influence of the alignment degree of CVD-grown carbon nanotubes on their functionalization and adsorption capacity

Oxygen functionalized multiwalled carbon nanotubes (CNTs) were prepared from aligned and bundle-like CVD-grown CNTs by chemical treatment with different reagents of increased oxidation degree. As the severity in the oxidation degree increases elimination of the amorphous carbon is observed. However, contrary to what was previously reported, aligned CNTs treated in less severe oxidation conditions they exhibit an increased number of oxygen containing functional groups (COH/CO groups). Meanwhile, when treated in the more severe oxidation conditions, they have the highest number of COOH groups due to the appearance of defects and shortening of the tubes. In the benzene adsorption in water, aligned CNTs display faster kinetics in all cases. The best adsorption capacity is achieved with aligned CNTs treated in very severe conditions possibly due to their enhanced solubility in water, which favors electrostatic interactions and π–π interactions between the benzene rings and the CNT walls.     

Liquid crystal behavior of single wall carbon nanotubes

Single wall carbon nanotubes are dispersed in water with the water-soluble polymer polyvinylpyrrolidone and the surfactant sodium dodecylbenzene sulfonate, and then deposited by evaporative deposition onto degeneratively-doped silicon wafer substrates. These deposits were examined by scanning electron microscopy, which revealed highly-ordered arrays of large single wall carbon nanotube bundles. Various solution concentrations were prepared and deposition conditions were varied to determine their affect on the single wall carbon nanotube arrays. These observations were related to existing lyotropic liquid crystal theory and theories explaining the behavior of carbon nanotubes in solution, which allowed for further development and interpretation of the phase diagram which describes the behavior of single wall carbon nanotubes in lyotropic liquid crystal systems, and how competing liquid crystal systems in the same solution directly affect the ordering of the single wall carbon nanotube arrays.     

Effect of number of walls on plasmon behavior in carbon nanotubes

We investigate the physical parameters controlling the low-energy screening in carbon nanotubes via electron energy loss spectroscopy and inelastic X-ray scattering. Two plasmon-like features are observed, one near 9 eV (the so-called π plasmon) and one near 20 eV (the so-called π + σ plasmon). At large nanotube diameters, the π + σ plasmon energies are found to depend on the number of walls and not on the radius or chiral vector. The observed shift with number of walls indicates a change in the strength of the screening and in the effective interaction at inter-atomic distances; thus this result suggests a mechanism for tuning the properties of nanotubes.     

Influence of surface layer conditions of multiwall carbon nanotubes on their electrophysical properties

We have investigated temperature σ(T) and magnetic field σ(B) dependences of the conductivity of multiwalled carbon nanotubes (MWNTs) with different average outer diameter d? and composite materials on the bases of these MWNTs in dielectric polymethyl methacrylate matrix (PMMA). It was shown that the percolation threshold of the electrical conductance for MWNT/PMMA composites lies in the range of concentration of MWNTs lower than 0.5 wt.%. From the joint analysis of σ(T) and σ(H) we have found that quantum corrections to the conductivity for interaction electrons is dominated in MWNTs with average outer diameters d? ～ 23 nm and MWNT/PMMA composite materials. We determined the constant of electron–electron interaction λ from quantum correction to σ(T) and σ(H). In the result we have found that λ depends on the concentration of MWNTs in MWNT/PMMA materials. This fact demonstrates that the interaction of the dielectric material of PMMA with surface atoms of MWNTs leads to the change of the λ in MWNTs. For MWNTs with average outer diameters d? ≤ 13 nm and for composite on the base of these MWNTs we have observed the domination of one dimensional variable range hopping conductivity (VRHC) at a temperature below 20 K. From the data of VRHC we estimated the density of localized states at the Fermi level N(E_F) and demonstrated that N(E_F) is decreasing in composite materials.     

Immobilization of antioxidant on nanosilica and the antioxidative behavior in low density polyethylene

Nanosilica was firstly modified with an aminosilane coupling agent (AEAPS) and then reacted with the reactive antioxidant, 3,5-di-tert-butyl-4-hydroxycinnamic acyl chloride (AO-Cl), to form a nanosilica-immobilized antioxidant, AO-AEAPS-silica. FT-IR, XPS and TGA measurements confirmed that the reactive antioxidant was chemically immobilized onto the nanosilica surface. SEM observation showed that the nanosilica-immobilized antioxidant was homogeneously dispersed into the matrix of low density polyethylene (LDPE). It has been found that the antioxidative efficiency of AO-AEAPS-silica was superior to the corresponding low molecular counterpart (AO), based on the measurement of the oxidation induction time (OIT) of the LDPE/AO-AEAPS-silica and the LDPE/AO compounds containing equivalent antioxidant component. The release of the antioxidant from LDPE films was evaluated by monitoring the OIT change upon water extraction, demonstrating that AO-AEAPS-silica retained high stability against migration.     

Gas-phase surface functionalization of multi-walled carbon nanotubes with vacuum UV photo-oxidation

For bulk processing of carbon nanotubes, an important first step in adhesion to the nanotubes is often liquid-phase functionalization through chemical oxidation with acids (e.g., nitric and sulfuric), peroxides and/or potassium permanganate. In comparison, gas-phase photo-oxidation can be an alternative to introduce oxygenated functional groups on the surfaces of carbon nanotubes without the generation of liquid waste. In the present study, vacuum UV photo-oxidation of multi-walled carbon nanotube (MWNT) paper was investigated downstream from an Ar microwave plasma. X-ray Photoelectron Spectroscopy (XPS) was used to detect the carbon- and oxygen-containing functional groups in the top 2–5 nm of the sample's surface. The current results are compared to previous investigations using MWNT powder and single-walled carbon nanotube (SWNT) paper showing decreased levels of oxidation in MWNT samples.     

Non-covalent/non-specific functionalization of multi-walled carbon nanotubes with a hyperbranched polyethylene and characterization of their dispersion in a polyolefin matrix

This communication reports the non-covalent, non-specific surface functionalization of multi-walled carbon nanotubes (MWCNTs) with a hyperbranched polyethylene (HBPE). The adsorption characteristics of the HBPE macromolecule on the MWCNTs were studied through an adsorption isotherm. Partial coverage of the nanotubes, estimated to be up to 25%, can be accomplished using this functionalization approach. The treated MWCNTs exhibited significantly improved dispersion within an ethylene–octene copolymer matrix, compared to the untreated fillers.     

The effect of carbon nanotubes on the rheology and electrical resistivity of polyamide 12/high density polyethylene blends

Different melt mixing sequences were applied to incorporate multiwalled carbon nanotubes (CNTs) into blends prepared from high density polyethylene (PE) and polyamide 12 (PA). Electron microscopy, rheology and electrical resistivity were used to characterize the morphology and microstructure. At a composition of 75PA/25PE, presence of CNT at the interface promoted by premixing the CNTs in the PE phase, resulted in finer phase morphology and a decrease in the resistivity of up to five decades relative to other mixing procedures used. At a composition of 25PA/75PE, premixing the CNT in the PA phase resulted in their segregation inside and around the PA domains and a four decade lower resistivity. Interestingly, compounds that yielded the lowest resistivity were also characterized by increased low frequency melt storage modulus (G′) which indicates the existence of a correlation between the two properties.     

Controlled surface functionalization of multiwall carbon nanotubes by HNO3 hydrothermal oxidation

Controlled surface functionalization is demonstrated by nitric acid hydrothermal oxidation on multiwall carbon nanotubes (MWCNTs). The formation and evolution of oxygen functional groups were systematically investigated as a function of the HNO₃ concentration on MWCNTs with different structural and morphological characteristics, employing temperature-programmed desorption coupled with mass spectrometry, thermogravimetry and differential scanning calorimetry, Raman spectroscopy and N₂ porosimetry analysis. Hydrothermal treatment provides controlled MWCNT modification by specific oxygen functionalities at amounts determined by the morphology, texture and crystallinity of the pristine materials. Hydrothermal oxidation competes well with the harsh boiling nitric acid treatment regarding the total amount of oxygen functionalities, while requiring much lower amounts of oxidizing agent and, most importantly, reducing amorphous carbon deposits on the MWCNT surface, a major drawback of aggressive liquid phase oxidation methods. Detailed pore structure analysis revealed a progressive increase of the surface area upon hydrothermal functionalization, whereas the mesopore structure varied consistently with the intrinsic MWCNT properties related to the packing of the nanotube bundles and the reduction of amorphous carbon. These advantageous features render nitric acid hydrothermal oxidation an efficient functionalization process to fine tune and optimize the surface chemistry of MWCNTs for target applications, circumventing the need for additional purification post-processing.     

Morphology and mechanical property changes in compatibilized high density polyethylene/polyamide 6 nanocomposites induced by carbon nanotubes

Addition of carbon nanotubes to immiscible polymer blends with co‐continuous morphology features to improve the electrical conductivity has attracted much attention in recent years; however, less attention has been paid to the effect of carbon nanotubes on the morphology and corresponding physical properties of immiscible polymer blends with typical sea‐island morphology. In this work, therefore, functionalized multiwalled carbon nanotubes (FMWCNTs) were introduced into an immiscible high density polyethylene/polyamide 6 (HDPE/PA6) blend which was compatibilized by maleic anhydride grafted HDPE (HDPE‐MA). The distribution of FMWCNTs and the phase morphologies of the nanocomposites were characterized using scanning electron microscopy and transmission electron microscopy. The crystallization and melting behaviors of the components were analyzed by differential scanning calorimetry, which is thought to be favorable for an understanding of the distribution of FMWCNTs. It is interesting to observe that the morphology of PA6 particles is very dependent on the method of preparation of the nanocomposites. Correspondingly, FMWCNTs exhibit an apparent reinforcement effect and/or an excellent toughening effect for the compatibilized HDPE/PA6 blend, depending upon their distribution state and the variation of PA6 morphology. This work proves that FMWCNTs have a potential application in further improving the mechanical properties of compatibilized immiscible polymer blends. Copyright © 2012 Society of Chemical Industry     

The effect of surface functionalization of carbon nanotubes on properties of natural rubber/carbon nanotube composites

The objective of this study was to prepare natural rubber composites filled with carbon nanotubes (CNTs) that show an electrical percolation threshold at very low CNT concentrations. Therefore, two methods of surface functionalization of CNTs were investigated to enable an improved dispersion of CNTs and chemical interaction between CNTs and rubber matrix. On one hand, the CNTs have been functionalized ex situ by acid treatment and silanization reaction with bis(triethoxysilylpropyl) tetrasulfide before mixing with the rubber and otherwise in situ functionalization was directly carried out during the processing of the composites in the internal mixer. The grafting of silane molecules onto CNT surface was established by Fourier transform infrared spectroscopy and scanning electron microscopy. Tensile tests revealed the outstanding properties of composites prepared by in situ silanization method. The in situ silanization led to a better dispersion of the CNTs and the formation of chemical linkages between CNT surface and rubber and this became manifest in higher reinforcement of the rubber, higher crosslink densities, and a lower electrical percolation threshold. It was also shown that the in situ silanization is retarding the vulcanization reaction. POLYM. COMPOS., 36:2113–2122, 2015. © 2014 Society of Plastics Engineer     

Influence of the surface chemistry of multi-walled carbon nanotubes on their activity as ozonation catalysts

Multi-walled carbon nanotubes (MWCNTs) with different surface chemical properties were prepared by oxidative treatments with HNO₃, H₂O₂ and O₂ to introduce oxygen-containing surface groups and by thermal treatments for their selective removal. The texture and surface chemistry of the MWCNTs were characterized by nitrogen adsorption, temperature programmed desorption (TPD) and pH at the point of zero charge. A deconvolution procedure of the TPD spectra was used to quantify the oxygenated surface groups. These materials were used as catalysts for ozone decomposition, and for the ozonation of oxalic and oxamic acids. Generally, all these catalytic processes are favoured by carbon nanotubes with low acidic character. MWCNTs were shown to exhibit higher activity for the ozonation of oxalic and oxamic acids, compared to activated carbon. Successive experimental runs of oxalic acid removal carried out with a selected MWCNT sample show that the catalyst suffers some deactivation as a result of the introduction of oxygenated groups on the surface. Therefore, the effect of the surface chemistry is mainly observed for the fresh catalysts.     

The method for surface functionalization of single-walled carbon nanotubes with fuming nitric acid

Surface functionalization of single-walled carbon nanotubes (SWCNTs) was carried out using fuming nitric acid as a NO₂ radical source. The surface double bonds of the SWCNTs reacted with the NO₂ radicals at 10–90 °C under sonication, and following treatment with aqueous NaOH yielded modified carbon nanotubes with high affinity for polar solvents such as dimethylformamide. The structure of the product was characterized using Fourier transform-infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis, and atomic force microscopy. FT-IR and XPS spectra revealed the product has OH groups (3400, 1200 cm⁻¹), which was expected due to the addition of NO₂ radicals to the surface double bonds and subsequent substitution with OH groups. C_1s curve fitting analysis of the XPS spectra was used to quantitatively determine the different functional groups on the surface, and the amount of COOH groups was found to be increased from 2.8% to 9.3% due to progressive oxidation by increasing the reaction temperature from 10 to 90 °C.     

Rheology and wire coating of high atomic number metal-low density polyethylene composites

The rheological properties of high atomic number metal-low density polyethylene composites were investigated. Tungsten, tungsten carbide, and lead powders were studied at concentrations up to 10 volume percent. Viscosity-shear rate, die swell-shear rate, and melt draw down to break data were, determined as functions of filler type, filler concentration, and particulate size at 200°C. The viscosity data were found to fit the Einstein relationship over the range of filler loadings and shear rates investigated. Tanner's equation was used to calculate the first normal stress difference from the die swell data. The effect of the fillers on the predicted first normal stress difference was contrary to previously observed experimental evidence. Melt draw down to break data was found to be very sensitive to filler contamination and correlated quite well with wire coating experiments. During low-speed wire coating runs coating quality was found to be seriously affected by small levels of contamination present in the fillers. Coating duality was determined by surface smoothness and uniformity.     

The effect of heterogeneity on the flow behavior on high density polyethylene

The effect of heterogeneity on the flow behavior of high density polyethylene (HDPE) has been studied by systematically homogenizing heterogeneous blends and observing the effect on the basic rheological parameters and on the extrudate surface appearance. Ample evidence is presented to show that heterogeneity causes substantial changes in the flow behavior although molecular parameters obtained through solution studies are unchanged. A simplified mathematical model which clearly illustrates the effects of the size of these flow units on the flow behavior is presented.     

Short chain branching distribution and thermal behavior of high density polyethylene

High-density polyethylenes with unimodal and bimodal molecular weight distribution have been fractionated according to crystallizability using preparative temperature rising elution fractionation. The molecular structure and thermal properties of the fractions with their whole polymers have been characterized. The average short chain branching content of the fractions obtained ranged from 0 to 8 branches per 1000 carbon atoms while that of the whole polymers is about 2 branches per 1000 carbon atoms. The bimodal resins have a slightly higher frequency of short chain branch in higher molecular weight species than in those of the unimodal resins. The short chain branching distribution as well as the low molecular weight species in the fractions seem to be important parameters to determine thermal behavior of the fractions. The fractions with the short chain branching content above 3 branches per 1000 carbon atoms showed a significantly different thermal behavior from those with less than 3 branches per 1000 carbon atoms. © 1996 John Wiley & Sons, Inc.     

Investigation on the thermal and crystallization behavior of high density polyethylene/acrylonitrile butadiene rubber blends and their composites

The properties of a blend containing a crystallizable component depend largely on the extent of crystallinity and the crystallization behavior of that component in presence of the other. Here, the semi crystalline high density polyethylene (HDPE) is blended with the amorphous elastomer, acrylonitrile butadiene rubber (nitrile rubber or NBR) and we focus mainly on the crystallinity of HDPE/NBR immiscible blends and its variation in the presence of compatibilizer and filler. The effect of blend ratio, compatibilizer concentration, dynamic vulcanization, and filler incorporation were carefully evaluated from the crystallinity measurements using differential scanning calorimeter and the basic aim of this work lies in tuning these conditions. This study allows the elucidation of the influence of crosslink density in regulating the crystallinity of thermoplastic elastomer blends. The scanning electron micrographs provide blend morphology from which the reduced domain size and the influence of NBR particles as heterogeneous nuclei for crystallization are evidenced especially at 5% compatibilizer concentration. The crystallinity of blends was observed to be high at 30 phr carbon black filler addition. Finally, the thermal stability of blends and their composites are also addressed and correlated with the crystallization effect. POLYM. ENG. SCI., 55:1203–1210, 2015. © 2014 Society of Plastics Engineers